JPS58219296A - Dispersant for coal-water slurry - Google Patents

Abstract

PURPOSE:A dispersant for preparing easily coal-water slurry having fluidity even at high concentration, containing a specific polyether derivative, a specified polyalkyleneimine (derivative), etc. CONSTITUTION:The desired dispersant for coal-water slurry containing (A) a polyether derivative shown by the formula (A is alcohol or phenol having one or more active hydrogens in the molecule; R1 is 3-4C alkylene oxide; l is 0-1,000; m is 50-1,000, etc.), having 5,000-100,000 molecular weight, (B) a copolymer derived from a polyalkylene glycol monoallyl ether, a maleic acid-based monomer and a monomer copolymerizable with it, and (C) a polyalkyleneimine (derivative).

Description

[Detailed description of the invention] -2- What is the invention? -i　m- Cover with a dispersant for water slurry.

More specifically, the present invention relates to a dispersant for dispersing coal powder in water to provide a highly concentrated coal-water slurry with fluidity.

Petroleum, which has traditionally been widely used as an energy source,
There are concerns that ICs will run out due to their high prices. Therefore, the challenge is to develop other energy sources that can provide a stable supply, and coal is once again becoming widely available. However, the biggest problem in using coal is transportation problems due to the fact that coal is solid.

Conventionally, mined coal is pulverized into powder, which is made into a coal-water slurry, which is fluidized and transported by pipeline.

- power, pipeline transportable COM (Coal -
Oil-M 1xture) is currently being tested, but since it uses oil, there are problems with stable supply and price, and high-temperature coal-water slurry is one of the coal utilization technologies in the future. It is seen as promising.

This technology of slurrying coal into water is about to be used in a very wide range of coal uses, such as direct combustion and gasification, in addition to the above-mentioned IC-3 - pipeline transportation of coal. This has become an important issue.

This coal-water slurry (in both cases, it is preferable to use a high-concentration slurry with low water content from the viewpoint of economy and pollution prevention. In particular, coal-water slurry can eliminate problems related to wastewater treatment and pollution. In the case of direct combustion, the water content of coal can be reduced by charging the water slurry of coal into a Reikron or turbulent flow burner and burning it directly in the furnace without dehydrating or drying the slurry. The reason for this need not be mentioned here, but is described in detail in Japanese Patent Application Laid-Open No. 57-21488.

However, when using known techniques to increase the concentration of coal powder, the slurry becomes significantly thickened and loses fluidity. On the other hand, if the temperature of coal powder in water is lowered to 111 degrees, transportation efficiency and combustion efficiency will decrease, and if the water slurry of coal is dehydrated and used, additional costs will be incurred in dehydrating and drying the T-culm. There are problems such as water pollution and pollution.

Conventionally, various dispersants for coal-water slurries have been proposed to solve such problems. For example, surfactants such as sodium oleate, sodium dodecyl benzene sulfonate, alkyl allyl sulfonate, polyoxyethylene alkyl phenyl ether, stearylamine hydrochloride, polyethylene glycol, polyacrylamide, cellulose, polyester, etc. Examples include water-soluble polymers such as sodium acrylate. However, both have insufficient fluidity and lack practicality.

The present inventors continued intensive research to solve the problems mentioned above in dispersants for coal-water slurries, and as a result, a certain polyether derivative copolymer was developed. The present invention was completed by discovering that a composition containing NN and compound (II) has excellent efficacy as a dispersant for coal-water slurry.

1- That is, the present invention provides a dispersant for easily producing a coal-water slurry having high concentration of C and fluidity.

That is, the dispersant for coal-water slurry of the present invention has the general formula % (%): (wherein A is alcohols, phenols, etc. having active hydrogen in the molecule from 1 to 1), Residues of amines, carboxylic acids, and their derivatives, [(1 is an alkylene A oxide residue having 3 to 4 carbon atoms, and the average number of moles added is θ ~
100, the sum is the average number of added moles of ethylene oxide, 5
Molecular weight 5 expressed as 0 to 1000, n is the number of functional groups)
000 to 100,000 polyether derivatives (1) (B) Polyalkylene glycol monoallyl ether (
A) A copolymer derived from a maleic acid monomer (B) and a monomer copolymerizable with these monomers (C) and (C) a group consisting of a polyalkylene imine and a polyalkylene imine derivative. A dispersant for a coal-water slurry is characterized in that it contains a selected 1-6-balance or two or more compounds (III).

The coal used for the coal-water slurry is, for example, anthracite,
Any type of coal cuttings, such as bituminous coal, sub-double blue coal, lignite, etc., can be used regardless of its type and origin, as well as its moisture content and chemical composition. Such coal may be milled to 200% by wet or dry crushing by conventional methods.
The standard for use is 50% by weight or more of meshicopus, preferably 70 to 80% by weight. Also, slurry W4r! J
is 60 to 90% by weight on a dry basis of pulverized coal, and if it is less than 60% by weight, it has no practical meaning due to economic efficiency, transportation efficiency, combustion efficiency, etc.

The dispersant for coal-water slurry of the present invention consists of 11 polyethers (1), a copolymer (If), and a compound (I).
II) can be obtained by the following method.

The polyether derivative (I) of the present invention having a molecular weight of 5,000 to 100,000 has the general formula AC(RIO)t(CH2CH2O)
mH'3n-7-, where Δ is a residue of a reaction starting material having various functional groups having at least one active hydrogen in the molecule,
This is subjected to an addition reaction with various alkylene oxides having 3 to 4 carbon atoms, such as propylene oxide and butylene oxide, using a conventional method under pressure using a catalyst such as an alkali or acid, and then ethylene oxide is added in the same manner. f1
Add to it.

R1 is an alkylene oxide residue having 3 to 4 carbon atoms.

t is 0 to 100 and represents the average number of added moles of alkylene oxide, and m is 50 to 1000 and is the average number of added moles of ethylene oxide. n is a number that is the same as or smaller than the functional number of the reaction starting material, and alkylene oxide may be bonded to all the functional numbers or only to a part of the functional numbers.

One type or two or more types of RIO may be used, and the arrangement thereof may be either block type and/or random type.

Further, a polyether derivative having a total of 10 to 800 carbon atoms (Jxn > times the carbon number of R□) can be used for female escorts.

The active hydrogen group referred to herein includes an alcoholic hydroxyl group, an amine group, a carboxylic acid group, and the like, and is a starting material containing one or more of these groups. Examples of these lunch breaks are as follows.

Alcohols containing one or more active hydrogen groups include ethyl alcohol, butyl alcohol, ocdyl alcohol, stearyl alcohol, ceryl alcohol, CI:2
-14 secondary alcohol, (Japan Catalyst Chemical product name Softanol), ethylene glycol, polyethylene glycol, propylene glycol,
Polypropylene glycol, butylene glycol, polybutylene glycol, butanediol, pentanediol, glycerin, butane 1-al, hequinanetriol, trimedylolpropane, triethanolamine, diglycerin, pentaerythritol, sorbitan,
Sorbitol, glucose, sucrose, partially saponified polyvinyl acetate, lerulose, starch, etc. are useful.

In addition, examples of amines containing one or more active hydrogen groups include dimedylamine, methylamine, thylamine, propylamine, butylamine, allylamine,
Amylamine, octylamine, dodecylamine, laurylamine, tetradecylamine, octadecylamine, tallow alkylamine, coconut alkylamine, aniline, toluidine, nitroamine, benzylamine, chloraniline, cyclohexylamine, ammonia, tallow propylene diamine, ethylene oxide, Tetramethylenediamine, phenylenediamine, benzidine, cyclohexyldiamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and the like are useful.

Examples of carboxylic acids containing one or more active hydrogen groups include acetic acid, lauric acid, oleic acid, stearic acid, oxalic acid,
Malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, azelaic acid, hybacic acid, dimer acid, phthalene diacetic acid, hemimellitic acid, trisolitic acid, trimesic acid, pyromellitic acid, ethylenediaminetetra Various derivatives such as acetic acid can also be used.

-10= Furthermore, examples of phenols containing one or more active hydrogen groups include phenol, bis71ol, cresol, 77alkylphenol, hydroquinone, and other compounds with aromatic water groups. Useful.

Furthermore, compounds containing different types of active hydrogen groups in the same molecule, such as lactic acid, malic acid, glycolic acid, mono-tanolamine, jetanolamine, amino acids, etc., can also be used.

Kikomei's copolymer (TI) is derived from polyalkylene glycol monoallyl 1-tyl (a), maleic acid monomer (g>83 and copolymerizable with these!!). A copolymer (II) having the general formula % can be used, preferably a copolymer (II) having the general formula % [ (where x and y are 0 or a positive integer, and x + y = 1
~ 100, MoC2H40÷ Unit: 11
- (-C3H60+ units may be bonded in any order.) Polyalkylene glycol monoallyl ether (a) represented by the general formula % formula % (However, in the formula, R2 and R3 are each hydrogen or represents a methyl group, and X and Y are each (-C2H40 mo(
C 3 H 6 0-handed qR' (Ra is hydrogen or carbon number 1
~20 alkyl groups, p and q are 0 or positive integers, p + q = 0 to 100, and moC2H
The 4 0÷ unit and the +C3H60+ unit may be combined in any order. ), -valent metal, divalent metal,
Represents an ammonium group or an organic amine group. ) Maleic acid monomer (1) and this-12
− A copolymer derived from a monomer (c) copolymerizable with
IT).

Polyalkylene glycol monoallyl ether (a) can be synthesized by a known method of directly adding dylene oxide and/or propylene oxide to allyl alcohol using an alkali such as KON or NaOl-1 as a catalyst. can. As long as it is represented by the above general formula, it can be used either as a single structure or as a mixture.

Maleic acid monomers are represented by the above general formula, but specifically include maleic acid, fumaric acid, sea salt, etc.
laconic acid, mesaconic acid and monovalent metal salts of these acids,
Divalent metal salts, ammonium salts, organic amine salts, and these acids and H O (-C 2 H 40 -) p (-C3
H60)-R4 <E, R4 is hydrogen or carbon number 1
~20 alkyl groups, p and q are 0 or positive integers, p→-q=O~100c, (-C3H60+
Mention may be made of esters of units with alcohols represented by (c2H, o units may be bonded in the order such as), such as -13-, for example, secondary alcohol ethoxy-1 -Monomarate can be suitably used. And one or more of these can be used.

In addition, monomers (c) that can be copolymerized with these include:
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid, monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts of these acids, alcohols, (meth)acrylamide, vinyl acetate, [2 Examples include propenyl, aromatic vinyl compounds such as styrene and p-methylstyrene, and vinyl chloride.
A species or two or more species can be used.

The copolymer (II) contains polyalkylene glycol monoallyl ether (a), a maleic acid monomer ([''), and a monomer that can be copolymerized with these (c) from 24 to 24% each.
75 mol%, 24 to 75 mol%, and 1 to 50 mol% (however, the total of components (a), (c), and (c) is 100 mol%). be. By falling within this ratio range, a dispersant for coal-water slurry with better performance than -14- is obtained.

In order to produce the copolymer (■), the monomer components may be copolymerized using a polymerization initiator. Copolymerization can be carried out by methods such as polymerization in a solvent or bulk polymerization.

Polymerization in a solvent can be carried out either batchwise or continuously, and the solvents used in this case include water; lower alcohols such as methyl alcohol, ]tyral alcohol, and isopyl alcohol; benzene, toluene, xylene,
Aromatic or aliphatic hydrocarbons such as cyclohexane, n-hexane; edyl acetate; aletone, methyl ethyl
Ton etc! Examples include a 7 ton compound. The solubility of the raw material monomer and the obtained copolymer (I), and the copolymer (I)
From the viewpoint of convenience when using TI), it is preferable to use at least one selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms. Among the lower alcohols having 1 to 4 carbon atoms, methyl alcohol, ethyl alcohol, and isopropyl alcohol are particularly effective.

When polymerization is carried out in an aqueous medium, a water-soluble polymerization initiator such as ammonium or alkali metal persulfate or hydrogen peroxide is used as the polymerization initiator. At this time, it is also possible to use 4 Jl of an accelerator such as thorium or sulfuric acid solution.

In addition, when using lower alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ethyl acetate, or chtonic compounds as solvents, peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide, etc. ;Aliphatic azo compounds such as azobisisobutyronitrile are used as polymerization initiators.

At this time, a promoter such as an amine compound may be used in combination. Furthermore, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from among the various polymerization initiators or combinations of polymerization initiators and accelerators mentioned above.

The polymerization temperature is adjusted appropriately depending on the solvent and polymerization initiator used, but it is usually carried out within the range of 0 to 120°C.

-16- Bulk polymerization is carried out using peroxides such as benzoylperA oxide and lauroyl peroxide; hydroperoxides such as cumenehyde [1] peroxide; aliphatic azo compounds such as azobisisobutyronitrile, etc., as polymerization initiators; It is carried out within a temperature range of ~150°C.

The copolymer (■) obtained in this way may be used after being neutralized with "C" and an alkaline substance as necessary. Such alkaline substances include -valent metals and divalent metals. Preferred examples include hydroxides, chlorides and carbonates: ammonia: organic amines.

Further, the molecular weight of the copolymer (IT) can be in a wide range, but it is preferably in the range of 500 to 50,000.

Compounds constituting the dispersant for coal-water slurry of the present invention (
The polyalkylene imine and polyalkylene imine derivative of IIT) can be produced by the method shown below.

The polyalkyleneimine of the present invention has at least 1-
17 It is a homopolymer or copolymer consisting of one type of alkyleneimine monomer. The alkyleneimine monomer is 1,2-
alkyleneimine (aziridine) and 1,3-alkyleneimine (azetidine), specific examples of which are 1-tyleneimine, 1゜2-propyleneimine, 1,3-alkyleneimine, and 1,3-alkyleneimine (azetidine).
-Propyleneimine, 1-methylaziridine, 2,2-
Dimethylaziridine, 1-ethylaziridine, 2-ethylaziridine, 2-n-propylaziridine, 2-isopropylaziridine, 2-n-butylaziridine, 2-
Isobutylaziridine, 1-(2-aminoethyl)aziridine, 1-(2-cyanoethyl)aziridine, 1-(
Examples include 2-hydroxyethyl)aziridine.

Homopolymerization and copolymerization of alkyleneimine monomers to polyalkyleneimines are promoted with acid catalysts and are easily carried out by methods known per se.

The form of copolymerization of the alkylene imine monomer may be any of random copolymerization, block copolymerization, graph l-copolymerization, and the like.

-18= Typical polyalkylene imines used in the present invention C are polyalkylene imines and polypropylene imines, which are manufactured on a commercial scale and are commercially available and can be used immediately.

Another preferred polyalkyleneimine is poly(ethyleneimine-propyleneimine) copolymer. The molecular weight of the polyalkyleneimine is not particularly limited, and a wide range of molecular weights from 600 to 10,000 is usually used, but a range of from 5,000 to 200,000 is particularly preferred.

Polyalkyleneimine derivatives are so-called modified polyesters made by reacting some of the amine groups of polyalkyleneimines with compounds having functional groups that are reactive with amino groups and making them soluble in water or a solvent mainly composed of water. Meaning alkyleneimine.

Specific examples of such polyalkylene imine derivatives include acrylamide and ? Polyalkyleneimine derivatives obtained by reacting a compound having an active double bond such as krylonyl-1-lyl: ■Polyalkyleneimine derivatives obtained by reacting a compound having an active double bond such as krylonyl-1-lyl; Alkyleneimine derivative; 1q by reacting with an aldehyde such as formaldehyde or acetaldehyde
Examples include polyalkylene imine derivatives obtained by reacting acid anhydrides such as succinic anhydride; polyalkylene imine derivatives obtained by reacting acid anhydrides such as succinic anhydride; however, the present invention is not limited to these. One type of polyalkyleneimine derivative may be used for neutralization, or two or more types may be used as a mixture. It can also be used in combination with polyalkyleneimine (jf).

The dispersant for coal-water slurry of the present invention contains a polyether derivative (1), a copolymer (IT), and a compound (Ill) as active ingredients, but the usage ratio of these is not particularly limited. However, polyether derivative (■)/
Copolymer (■)/Compound (III); 20-95%
A ratio of /3 to 50% by weight/2 to 30% by weight exhibits particularly excellent performance.

The dispersant for coal-water slurries of the present invention is used for pulverized coal-water slurries, but the fields in which it is added are not limited to specific areas. From the point of view, 0 for pulverized coal (dry base)
．． It is used in a proportion of 0.05 to 3% by weight, preferably 0.1 to 2% by weight.

In order to use the dispersant for charcoal-water slurry of the present invention, the polyether derivative (1), copolymer (TI) and compound (It) are mixed in advance and then added at the time of slurry preparation. or a poly-ep-thyl derivative (
J>, the copolymer (TI>) and the compound ([I[) may be added separately during slurry preparation.

Alternatively, it may be mixed with coal in advance to form a slurry, or it may be dissolved in water in advance. Furthermore, as the dispersant and slurry-forming equipment, any material for slurrying coal in water may be used.

The scope of the present invention is not limited by these addition methods and slurry-forming methods.

Next, comparative examples and examples of the dispersant for coal-water slurry of the present invention will be given and explained in more detail. However, the present invention is of course limited to these. isn't it.

In the examples, unless otherwise specified, % means % by weight, and parts represent parts by weight.

Preparation of Copolymer JT-1 Poly J-ethylene glycol monoallyl ether (average of 5 ethylene oxide units per molecule) was placed in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, gas inlet tube, and reflux condenser. 3,173 parts (containing 100% alcohol) and 88.5 parts of water were added, and the inside of the reaction vessel was purged with nitrogen while stirring, and heated to 95° C. in a nitrogen atmosphere. Then, anhydrous malein 913
9.3 parts and 11.1 parts of ammonium persulfate were added to 209 parts of water.
1 part of the aqueous solution and 62 parts of styrene were added in parallel.
Added in 20 minutes. After the addition is complete, add another 27.3 parts of 20
% ammonium persulfate solution was added over 60 minutes. After the addition was completed, the temperature in the reaction vessel was maintained at 95° C. for 90 minutes to complete the polymerization reaction, and an aqueous copolymer solution was obtained. then 40
% caustic soda aqueous solution was added to perform neutralization, and an aqueous solution of copolymer "■-1" was obtained.

= 22 - Pl-1 and viscosity of this aqueous solution of copolymer H-1 are shown in Table-
It was as shown in 1.

Preparation of Copolymer H-2 Polyethylene glycol monoallyl ether (10 molecules per molecule on average
(containing dylene A oxide units) 349 parts and 64 parts of water.
7 parts of the mixture was added, and the inside of the reaction vessel was purged with nitrogen while stirring, and heated to 65° C. in a nitrogen atmosphere.

Then 116 parts of maleic acid and 24 parts of ammonium persulfate
．． An aqueous solution of 112 parts of the sodium hydrogen trioxide dissolved in 44.8 parts of water and 258 parts of vinyl acetate were added over 120 minutes each. After the addition was completed, the temperature in the reaction vessel was maintained at 65° C. for 120 minutes to complete the polymerization reaction, and an aqueous copolymer solution was obtained.

Next, neutralize by adding a 40% aqueous solution of caustic soda,
19 for an aqueous solution of copolymer H-2.

The P)-1 and viscosity of this aqueous solution of copolymer ff-2 were as shown in Table-1.

Preparation of copolymer JT-3-23 Temperature agent, stirrer, dropping U-t, gas introduction pipe and i! In a glass reaction vessel equipped with a flow cooling device, 149.6 parts of polyethylene glycol monoallyl ether (containing an average of 10 ethylene oxide units per molecule) and 6 parts of polypropylene glycol monoallyl ether (containing an average of 5 ethylene oxide units per molecule) were added. containing propylene oxide units) 349 parts,
58 parts of maleic acid, 1 hydroxyethyl methacrylate
11 of a mixed solution consisting of 13 parts, 596 parts of isopropyl alcohol, and 71 parts of benzoyl peroxide.
After charging 18 parts, the inside of the reaction vessel was replaced with nitrogen while stirring, and heated to the boiling point of the mixed solution in a nitrogen atmosphere. Thereafter, the remaining 6874 parts of the mixed solution was added over 120 minutes. After the addition is complete, maintain the temperature in the reaction vessel at the boiling point for 120 minutes to -C
The polymerization reaction was continued. In all cases, the temperature inside the reaction vessel was returned to room temperature, 77 parts of benzoyl peroxide was added and heated again to distill off the isopropyl alcohol, and deionized water and 40% caustic sorta aqueous solution were added to perform neutralization. An aqueous solution of polymer II-3 was obtained.

-24- The P)-1 and viscosity of this aqueous solution of copolymer Tl-3 were as shown in Table-1.

Polyalkylene glycol monoallyl ether (average amount per molecule (containing 3 -L tyrene oxide units <l and 2111 il of propylene oxide units) 220.6 parts,
Secondary alcohol 31 ethoxylene-1 ~ (softanol-30 Nippon Shokubai Chemical Industry (IslgA>monomale-1)
~344, 3 parts, 8.3 parts of styrene, 2414 parts of isopropyl alcohol, and 16.9 parts of benzoyl peroxide.
246.5 parts of the mixed solution consisting of 1.0 parts were charged, and while stirring, the inside of the reaction vessel was checked for nitrogen and heated to the boiling point of the mixed solution in a nitrogen atmosphere. Thereafter, the remaining 575 parts of the mixed solution was added over 120 minutes. After the addition was completed, the temperature in the reaction vessel was maintained at the boiling point for 120 minutes to continue the polymerization reaction. Thereafter, the temperature inside the reaction vessel was returned to room temperature, 16.9 parts of benzoyl peroxide was added and heated again, and the isopropyl alcohol was distilled off to give a copolymer. ? /C. Then, neutralization was carried out by adding a 40% aqueous solution of caustic soda and deionized water, and 1N of an aqueous solution of copolymer 11-4 was added.

The pH and viscosity of this aqueous solution of copolymer H-4 are shown in Table-1.

Table-1 Aqueous solution 31.7 containing predetermined amounts of various dispersants shown in Example Table-2
During Q, pass 79% of the 200 mesh sieves -26
- Daido charcoal crushed by sea urchin 68.3 (+ (moisture content 5.1%)
) is added little by little at room temperature while stirring. After adding the entire amount, use a small fir kina (manufactured by Tokushu Kikaku) to 10.0
OORP M, the coal-water slurry was prepared by stirring for 2 minutes, the viscosity was measured at 25°C, and the fluidity was evaluated.

The results are shown in Table-2. Low viscosity indicates good fluidity.

The substances of compound (I'll) shown in Table 2 are as follows.

1'1l-1: Polyethyleneimine (molecular weight approximately 70,000) 1
11-2: Polypropylene imine (molecular weight approximately 20,000) ■-3: Ethyleneimine (25 mol)/12-propylene imine (1.0 mol) copolymer, molecular weight approximately 40,000) ■-4; Acryloni (-lyl addition) <0.1 mol) Polyethyleneimine (approx. 50,000 molecules) -27-

Claims (4)

[Claims] (1) (△) General formula % Formula %) (In the formula, A is the residue of alcohols, 7 alcohols, amines, carboxylic acids, and their derivatives having one or more active hydrogens in the molecule. , R1 is an alkylene oxide residue having 3 to 4 carbon atoms, and t is the average number of added moles thereof, 0 to 100.
, m is the average number of moles of ethylene oxide, 50
-1000. (n is the number of functional groups) Polyether derivative (I) with a molecular weight of 5,000 to 100,000, (B) polyalkylene glycol monoallyl ether
a), a maleic acid monomer (b), and a copolymer derived from a single 1-hanging body (c) copolymerizable with these (II) and (C) polyalkylene imine and polyalkylene imine 1. A dispersant for coal-water slurry, comprising one or more compounds (III) selected from the group consisting of derivatives. (2) In the polyether derivative (I), the total number of carbon atoms of R□ <t, xn> times and the number of carbon atoms of A is 10 to 80
0. The dispersant according to claim 1, wherein the dispersant has a molecular weight of 0. (3) Polyalkyleneimine is polyethyleneimine,
The dispersant according to any one of claims 1 to 2, which is polypropylene imine. (4) The dispersant according to claim 1, wherein the polyalkylene imine or polyalkylene imine derivative has an average molecular weight of 5,000 to 200,000.